Classifications

• • H—ELECTRICITY
  • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
  • H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
  • H02J3/00—Circuit arrangements for ac mains or ac distribution networks
  • H02J3/38—Arrangements for parallely feeding a single network by two or more generators, converters or transformers
  • H02J3/381—Dispersed generators
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
  • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
  • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
  • C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
• • H—ELECTRICITY
  • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
  • H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
  • H02J15/00—Systems for storing electric energy
• • H—ELECTRICITY
  • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
  • H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
  • H02J15/00—Systems for storing electric energy
  • H02J15/008—Systems for storing electric energy using hydrogen as energy vector
• • H—ELECTRICITY
  • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
  • H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
  • H02J3/00—Circuit arrangements for ac mains or ac distribution networks
  • H02J3/12—Circuit arrangements for ac mains or ac distribution networks for adjusting voltage in ac networks by changing a characteristic of the network load
  • H02J3/14—Circuit arrangements for ac mains or ac distribution networks for adjusting voltage in ac networks by changing a characteristic of the network load by switching loads on to, or off from, network, e.g. progressively balanced loading
• • H—ELECTRICITY
  • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
  • H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
  • H02J3/00—Circuit arrangements for ac mains or ac distribution networks
  • H02J3/28—Arrangements for balancing of the load in a network by storage of energy
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/02—Processes for making hydrogen or synthesis gas
  • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/06—Integration with other chemical processes
  • C01B2203/066—Integration with other chemical processes with fuel cells
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
  • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
  • C01B2203/1205—Composition of the feed
  • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
  • C01B2203/1235—Hydrocarbons
  • C01B2203/1241—Natural gas or methane
• • H—ELECTRICITY
  • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
  • H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
  • H02J2300/00—Systems for supplying or distributing electric power characterised by decentralized, dispersed, or local generation
  • H02J2300/30—The power source being a fuel cell
• • H—ELECTRICITY
  • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
  • H02J—CIRCUIT ARRANGEMENTS OR SYSTEMS FOR SUPPLYING OR DISTRIBUTING ELECTRIC POWER; SYSTEMS FOR STORING ELECTRIC ENERGY
  • H02J2310/00—The network for supplying or distributing electric power characterised by its spatial reach or by the load
  • H02J2310/10—The network having a local or delimited stationary reach
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
  • Y02B70/00—Technologies for an efficient end-user side electric power management and consumption
  • Y02B70/30—Systems integrating technologies related to power network operation and communication or information technologies for improving the carbon footprint of the management of residential or tertiary loads, i.e. smart grids as climate change mitigation technology in the buildings sector, including also the last stages of power distribution and the control, monitoring or operating management systems at local level
  • Y02B70/3225—Demand response systems, e.g. load shedding, peak shaving
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E70/00—Other energy conversion or management systems reducing GHG emissions
  • Y02E70/30—Systems combining energy storage with energy generation of non-fossil origin
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/10—Process efficiency
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P90/00—Enabling technologies with a potential contribution to greenhouse gas [GHG] emissions mitigation
  • Y02P90/50—Energy storage in industry with an added climate change mitigation effect
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y04—INFORMATION OR COMMUNICATION TECHNOLOGIES HAVING AN IMPACT ON OTHER TECHNOLOGY AREAS
  • Y04S—SYSTEMS INTEGRATING TECHNOLOGIES RELATED TO POWER NETWORK OPERATION, COMMUNICATION OR INFORMATION TECHNOLOGIES FOR IMPROVING THE ELECTRICAL POWER GENERATION, TRANSMISSION, DISTRIBUTION, MANAGEMENT OR USAGE, i.e. SMART GRIDS
  • Y04S20/00—Management or operation of end-user stationary applications or the last stages of power distribution; Controlling, monitoring or operating thereof
  • Y04S20/20—End-user application control systems
  • Y04S20/222—Demand response systems, e.g. load shedding, peak shaving

Definitions

• the invention relates to a method for continuously performing one or more heat-consuming processes, which is characterized in that the at least one heat-consuming process is electrically heated, the maximum temperature in the reaction zone of the heat-consuming process is greater than 500 ° C, at least 70% of the Products of the at least one heat-consuming process are continuously processed further in downstream processes and / or are fed to a local energy carrier network and the electrical energy required for the at least one heat-consuming process is obtained from an external power grid and from at least one local power source, wherein the at least one local power source is fed at least 50% of its annual energy requirement from at least one local energy carrier network and a maximum of 50% of its annual energy requirement is fed with products from the heat-consuming process, with im at least one local energy carrier network is stored as the energy carrier natural gas, Naptha, hydrogen, synthesis gas and / or water vapor, the at least one local energy carrier network being fed with at least one further product and / or by-product from at least one further chemical process and the local energy carrier network has a total capacity of at least 5
• US 4,776,171 describes an energy generation and management system consisting of several renewable energy sources and several energy storage sources, as well as several control and distribution stations in order to meet the needs of the industry.
• US 2011/0081586 describes a combination of a renewable energy source with an electrochemical or electrolytic cell in which the electrochemical or electrolytic cell can compensate for the fluctuations in the renewable energy source and thus makes it continuously usable.
• US 2008/0303348 discloses a power plant that is based exclusively on renewable energies and yet enables demand-dependent control.
• US 2008/0303348 loading describes the combination of wind energy, solar energy and the energy obtained from the combustion of biomass. It describes how the power plant can switch between the three energy sources smoothly and spontaneously in order to meet the industry's needs at low cost at any time.
• the focus of these disclosures is to be able to offer consumers the electricity they need - despite the use of fluctuating renewable energy.
• the customer specifies the amount of electricity produced and the weather determines the proportion of electricity generated from renewable sources.
• US 2012/0186252 describes a method for generating and distributing electricity which is not exclusively adapted to the needs of external customers.
• a conventional power plant is operated with fossil and / or renewable fuels and the electricity generated is fed into the public electricity network as long as electricity is required.
• the electricity generated is used internally to generate hydrogen, which can then be converted into the renewable fuel methane with carbon dioxide in a Sabatier process.
• the hydrogen generator can thus dampen the slow dynamics of the local power source due to fluctuating production output.
• electricity from the public grid is used to operate the internal hydrogen generator.
• the hydrogen generator is therefore operated depending on the electricity demand and electricity supply; When there is little electricity demand, the electricity for the generator comes from a local source and in times of excess electricity from the public power grid.
• the disadvantage of this method is that the hydrogen generator is operated as a heat-consuming process with fluctuating production output, since this serves to adapt the output of the conventional power plant to the needs of the network.
• US 4,558,494 describes the direct use of solar energy for the production of ammonia.
• the heat required for this endothermic process is provided by a heat transfer fluid that is heated by solar energy when solar energy is available and by burning the ammonia produced when solar energy is not available.
• US 4,668,494 accordingly discloses the use of two separate energy sources, a solar and an oxidative, for an endothermic chemical process; the use of an electrical power source is not described.
• control power a distinction is made between secondary control power and minute reserve power depending on the required activation time.
• the provision of a capacity as control power, the so-called control power reserve is remunerated, regardless of whether the capacity is used or not.
• the so-called control power reserve is remunerated, regardless of whether the capacity is used or not.
• the remuneration for the provision of control power for primary control power, secondary control power and minute reserve power was just under € 200 million (2017 monitoring report by the Federal Network Agency).
• the remuneration for using the control power is determined by the balance energy price.
• the balancing energy price can be offered on the electricity market well below its production costs or at prices that are lower in relation to its energy content than for a fossil fuel with the same calorific value, or for free (i.e. without consideration) or even at negative prices.
• the mean value of the balancing energy price was -14.12 € / MWh. This means that consumers who purchased excess electricity received an additional credit. This total of credits amounted to around € 10.78 million in 2016.
• the Renewable Energy Sources Act guarantees the producers of renewable energies priority feed-in into the power grid. If, despite all network optimization and network expansion measures, situations arise in which a down-regulation of the renewable electricity producers cannot be avoided due to excess capacities or a lack of transport capacities, this must be remunerated by the network operator in whose network the cause of the down-regulation is justified. In 2016, 3743.2 GWh were affected by these so-called feed-in management measures, which had to be remunerated at around € 643 million (2017 monitoring report by the Federal Network Agency).
• the start-up time of lignite and hard coal power plants is several hours.
• the start-up time of combined cycle power plants is around one hour.
• the power plant efficiency is 55% to 60% in combined cycle power plants, 42% to 47% in hard coal power plants, 38% to 43% in lignite power plants and 34% to 40% in gas turbine power plants.
• All thermal power plant types have a usable load range between 40% and 90% of the maximum output, with the power plant efficiency being highest in the full load range. Taking these features into account, the task arises to connect consumers with a large, continuous power requirement to the power grid so that base load power plants can work as continuously as possible at high loads.
• Control circuits of different speeds are used for frequency control in electrical networks: primary control with a response time of less than 30s, secondary control with a response time of less than 5 minutes and finally tertiary control, which allows a longer response time.
• the primary control is triggered automatically and has a direct effect on the operating status of running power plants.
• the secondary control is also triggered automatically and can activate reserve capacities from standby mode.
• the tertiary regulation (or minute reserve) is usually activated by organizational measures.
• the secondary control and the minute reserve can be positive (with increased power requirement) or negative (with reduced power requirement).
• the positive secondary control and the minute reserve are usually activated by switching on reserve power plants.
• the negative minute reserve requires one Energy consumers.
• Heat storage systems can store energy in the form of heat.
• the heat can be obtained from, for example, flue gases from combustion processes, from electrical heaters, from solar collectors.
• Heat accumulators can be divided into three main categories. Sensitive heat storage systems store heat as a noticeable increase in temperature; with latent heat storage systems, the energy is stored in the phase transition of the storage medium. Thermochemical and sorption storage systems store heat energy reversibly as chemical reaction or ad / absorption heat. Liquid or solid materials with a high heat capacity are used as sensible heat storage.
• Common liquids are water for the temperature range from 0 ° C to 100 ° C, heat transfer oil for the temperature range from 0 ° C to 400 ° C, nitrate salts for the temperature range from 250 ° C to 570 ° C, carbonate salts for the temperature range from 450 ° C C to 850 ° C and sodium for the temperature range from 100 ° C to 800 ° C.
• Common solid heat stores are moist gravel fillings for the temperature range from 0 ° C to 100 ° C, concrete for the temperature range from 0 ° C to 500 ° C, Gravel or sand, granite, or iron alloys for the temperature range from 0 ° C to 800 ° C and bricks for the temperature range from 0 ° C to 1000 ° C.
• latent heat storage Materials that change their aggregate state in the work area either between solid and liquid or between liquid and gaseous are used as latent heat storage.
• Common materials are water, which is used at 0 ° C as a solid-liquid latent heat store and in the temperature range from 100 ° C to 350 ° C as a vapor-liquid latent heat store.
• Other solid-liquid latent heat storage systems are raw paraffin at around 34 ° C, eicosan at around 37 ° C, lauric acid at around 44 ° C, myristic acid at around 54 ° C, stearic acid at around 70 ° C, mirabilite (Na 2 SO 4 10H 2 O) at around 32 ° C, pentahydrate (Na 2 S 2 0 3 5H 2 0) at approx.
• Thermochemical storage systems use reversible reactions. Such reactions can include the dehydration of metal hydrides, for example MgH 2 , Mg 2 NiH 4 , Mg 2 FeH 6 , the dehydration of metal hydroxides, for example Mg (OH) 2 , Ca (OH) 2 , Ba (OH) 2 , the decarboxylation of metal carbonates , for example MgC0 3 .
• PbC0 3 , CaC0 3 , BaC0 3 the partial reduction of oxides of multivalent metals, for example Pb0 2 , Sb 2 0 5 , Mn0 2 , Mn 2 0 3 , CuO, Fe 2 0 3 , be.
• Salt hydrates for example MgS0 4 -7H 2 0, MgCl 2 -6H 2 0, CaCl 2 -6H 2 0, CuS0 4 -5H 2 0, CuS0 4 -H 2 0, or ammoniates of metal chlorides, for example CaCl 2 - are used as sorption storage.
• 8NH 3 , CaCl 2 -4NH 3 , MnCl 2 -6NH 3 were used.
• endothermic high-temperature processes that deliver hydrogen-rich products for example steam reforming or pyrolysis of natural gas, can be used as thermochemical storage. The hydrogen can be used both materially and energetically.
• Solar thermal power plants are an important area of heat storage. Molten salt, thermal oils and concrete storage tanks are used here. Furthermore, heat accumulators, used in power plants, can improve load flexibility in terms of minimum load and load change rate. For example, steam accumulators are used to provide control power.
• Electric power is currently used as the energy source of choice mainly for non-catalyzed gas / solid and solid reactions when large heat flows have to be entered at a very high temperature level.
• Typical applications are metallurgical furnaces [Ullmann: Metalurgical Furnaces].
• the only relevant gas phase processes are the plasma process for the production of acetylene from methane [Baumann, Angewandte Chemie, Edition B, Volume 20 (1948), pages 257-259, 1948] and the process for the production of reducing gases in the steel industry.
• electrical energy sources in gas phase processes from which, however, it has not yet been possible to develop any applications that can be used economically on an industrial scale.
• HCN hydrocyanic acid
• No. 7,288,690 describes a method for steam cracking of hydrocarbons, the cans being heated electrically.
• the improvement achieved by this invention is essentially the use of combined heat and power to generate heat and electricity at the same time from the combustion of a fuel.
• the fuel is preferably burned in a gas turbine that drives a generator.
• the one with it The electricity generated is used to heat the cans.
• the sensible heat contained in the combustion exhaust gases is used to preheat the feed mixture.
• the disadvantage of this solution is the coupling between the energy flows that are available for the electrical heating of the cans and for the preheating of the feed mixture. This coupling forces a suboptimal operating state of one of the process stages.
• the applicability of the invention is limited to non-heat-integrated processes.
• DE 102013209883 describes an integrated system for the electrochemical production of hydrocyanic acid with a discontinuous mode of operation, which can adapt its process performance to the external electricity supply by means of a weather forecast.
• DE 102012023832 describes an integrated, dynamic system for the electrochemical production of ethyne.
• the respective reactor is supplied with electrical energy via the external power grid and a local power source, with the local power source using a hydrogen-rich waste gas stream from hydrogen cyanide or ethyne production directly without intermediate storage for power production.
• Fuel cell and gas turbine power plants or combined cycle power plants can be used as power sources.
• Hydrocarbons and hydrogen are stored; These storage facilities have a hydrogen capacity that can be produced in 48 hours with the help of this system (around 5000 MWh).
• the hydrocarbons and hydrogen are fed from the storage facility into the natural gas network, taking into account the Wobbe index, or the hydrocarbons are fed back into the reactor. Use of the stored gases to operate the local power source is not disclosed.
• the dynamic mode of operation has the disadvantage in terms of operational safety, in that decomposable, highly reactive substances such as ethine and hydrogen cyanide have to be stored in order to compensate for the fluctuating production quantities.
• a further disadvantage is that the reactors experience strong temperature fluctuations due to the frequent start-up and shutdown processes, which have a negative effect on their service life and operational safety.
• a further disadvantage is that the device for introducing a gas into a natural gas network requires considerable additional expenditure on machines and apparatus that are not required for carrying out the process.
• Another disadvantage is that the process dynamics, in particular those of the separation stages and the planning intervals of the weather forecast, are too long to use the process as a secondary or tertiary reserve.
• Some important heat consuming processes are high temperature processes, i.e. Processes that are carried out at temperatures between 500 and 2,500 ° C.
• Representatives of these very energy-intensive processes are steam and dry reforming, dehydrogenation, for example from primary alcohols to aldehydes, from secondary alcohols to ketones, from alkanes to alkenes and from cycloalkanes to cycloalkenes, and the production of hydrocyanic acid by formamide cleavage or from methane and ammonia, the production of nitrogen monoxide from air, the vapor splitting or the pyrolysis of hydrocarbons and the thermolysis of water.
• Steam and dry reforming are processes for the production of synthesis gas, a mixture of carbon monoxide and hydrogen, from carbon-containing energy sources such as natural gas, light gasoline, methanol, biogas or biomass and water or carbon dioxide.
• the vapor cracking of hydrocarbons is the industrially established process for the production of short-chain olefins, in particular ethylene and propylene, and aromatic compounds from hydrocarbon-containing energy sources such as shale gas, naphtha and liquefied gases. This process takes place with short reaction times in a kinetically controlled regime.
• Pyrolysis is a process in which hydrocarbons are converted into their stable end products, carbon and hydrogen. This process takes place in the equilibrium-controlled regime with longer dwell times.
• endothermic high-temperature processes such as steam cleavage or steam reforming require a heat input that is significantly higher than the heat requirement of the endothermic reaction.
• the excess of the input heating power is 80% to 200% based on the heat demand of the endothermic reaction.
• the excess heating power is exported to downstream stages, for example to generate steam at different pressure levels.
• the thermal efficiency of such systems can be increased to 90% or more.
• the disadvantage of these processes is that the primary energy requirement and the associated greenhouse emissions are significantly higher than the actual requirement of the high-temperature reaction.
• Another disadvantage results from the rigid energetic Coupling between different systems of a connecting site; These couplings mean that the operating point of the individual systems can only be set within narrow limits.
• 2014/090914 is the first reference to use chemical processes as a minute reserve using excess electricity.
• a method is described for carrying out heat-consuming high-temperature processes, with the total energy required as an annual average coming from at least two different energy sources, at least one electrical energy source, which provides between 0 and 100% of the total energy required, in particular using excess electricity, and one further non-electrical energy source, which may provide the rest of the energy required.
• a major challenge with this concept is the load on the equipment when switching between the two energy sources and, furthermore, switching over with as little loss as possible and dynamically, i.e. without loss of turnover or selectivity.
• Another disadvantage of this solution is that it may be necessary to install two independent devices for generating heat in the area of the process that are exposed to high temperatures. This increases the complexity and susceptibility of the process to defects.
• EP3249027 claims a reduced-emissions process for the production of olefins by steam cracking of hydrocarbons.
• the cans can be heated both by the combustion heat of a fuel and by electrical heat.
• the object of the present invention is therefore to make use of chemical high-temperature processes in the sense of energy change as a sink for excess electricity from regenerative energy sources. Another task is to use chemical processes as energy consumers with a negative secondary control and / or minute reserve for frequency control in provide electrical networks. Another task is to make the endothermic chemical process so flexible that it can choose the power source depending on the wholesale electricity price, thus enabling economic optimization.
• Another task is to keep the setpoint deviation of the power input into the endothermic process so low when switching between the power sources that the production output is not changed. Another task is that the local power sources have the highest possible efficiency and the lowest possible CO 2 emissions.
• Another task is to integrate the local power sources into the material and heat network of the endothermic process. If local power sources are used that can be switched on or off quickly, energy sources must be available that can be switched on or off quickly enough.
• the present invention should, despite the use of excess electricity, equalize the production rate of the heat-consuming processes concerned and minimize the load on the machines and apparatus.
• the present invention should improve the plannability of downstream processes in that the utilization of the upstream heat-consuming process is controlled by the demand of the downstream processes, regardless of the availability of excess electricity.
• the plant and the process should continue to have the highest possible efficiency. Furthermore, the method according to the invention should be able to be carried out using the conventional and widely available infrastructure. In addition, the process should be able to be carried out with as few process steps as possible, and these should be simple and reproducible.
• fluid media can be used as energy carriers, which are distributed over the entire location via connected pipeline networks and storage tanks (local energy carrier networks).
• energy carriers can be raw materials such as natural gas or liquid gas, basic products such as hydrogen or synthetic segas and auxiliary materials such as steam or compressed air.
• local energy carrier networks offer a sufficiently large capacity to store mechanical energy, heat and / or combustible materials and to make them available without delay for the supply of local power sources when required.
• a method for the continuous implementation of one or more heat-consuming chemical processes which is characterized in that the at least one heat-consuming process is electrically heated, the maximum temperature in the reaction zone of the heat-consuming process is greater than 500 ° C is, at least 70% of the products of the at least one heat-consuming process are continuously processed in downstream processes and / or are supplied to a local energy carrier network and the required electrical energy for the at least one heat-consuming process from the external power grid and from at least one local power source is purchased, with the at least one local power source being fed at least 50% of its annual energy requirement from at least one local energy carrier network and a maximum of 50% of its annual energy requirement with products from the heat consuming process is fed without intermediate storage, with natural gas, naphtha, hydrogen, synthesis gas and / or water vapor being stored as energy carriers in at least one local energy carrier network, the at least one local energy carrier network with at least one further product and / or by-product from at least one further chemical process is fed and the local energy carrier network has
• the present invention also relates to the use of at least one local energy carrier network at chemical sites for storing electrical energy, natural gas, liquid gas or naphtha, hydrogen, ammonia, synthesis gas, ethylene, propylene, lean gas, compressed air and / or steam being used as energy carriers and wherein the energy carrier network has a total capacity of at least 5 GWh.
• the local energy carrier networks can be divided into networks / storage for heat carriers, such as Water vapor, networks / storage for intermediate products, such as Hydrogen and synthesis gas and networks / storage for raw materials, such as Natural gas and naphtha. At least two local energy carrier networks are preferably used.
• At least two different local energy carrier networks are preferably used for energy carriers selected from the group consisting of heat carriers, preferably water vapor, intermediates, preferably hydrogen and / or synthesis gas, especially hydrogen and raw materials, preferably natural gas and naphtha, especially natural gas. Preference is given to using the two combinations of heat carriers and intermediates or the three combinations of heat carriers, intermediates and raw materials.
• at least 50%, preferably 70%, in particular 90% of the products of the at least one heat-consuming process are continuously processed further in downstream processes and / or fed to a local energy carrier network.
• the percentage product range is preferably 50 to 100%, preferably 70 to 100%, in particular 90 to 100%.
• the downstream process is understood to mean the subsequent conversion of the products from the heat-consuming process to other products.
• the at least one local power source is advantageously fed to at least 50% of its annual energy requirement from a local energy carrier network; preferably at least 70%, more preferably at least 80%, more preferably at least 90%.
• the percentage range is advantageously 50 to 100, preferably 70 to 100, more preferably 80 to 100, in particular 90 to 100.
• the at least one local power source is particularly preferably fed exclusively from the local energy carrier network.
• the at least one local power source is advantageously supplied with a maximum of 50% of its annual energy requirement, preferably a maximum of 20%, particularly preferably a maximum of 10%, with products that come directly from the heat-consuming process.
• the percentage range is advantageously 50 to 0, preferably 20 to 0, in particular 10 to 0.
• the local energy carrier networks are advantageously each fed with at least one further product and / or by-product from at least one further chemical process.
• These other chemical processes are, for example, olefin processes, Synthe segas processes, partial oxidations, pyrolysis of hydrocarbons, water electrolysis, metallurgical processes and / or hydrogenations.
• the hydrogen energy carrier network is fed from processes such as steam cracking, steam reforming, methane pyrolysis, styrene synthesis, propane dehydrogenation, synthesis gas production, and formaldehyde synthesis.
• the steam energy carrier network from processes such as steam cracking, steam reforming, acetylene process, synthesis gas production, acrylic acid synthesis, phthalic anhydride synthesis, maleic anhydride synthesis, ethylene oxide synthesis, formaldehyde synthesis is fed.
• the hydrocarbon energy carrier network is fed from the raw materials naphtha, natural gas and liquid gas.
• the endothermic processes such as steam cracking, steam / dry reforming, styrene synthesis, propane dehydrogenation, butane dehydrogenation, hydrocyanic acid synthesis, methane pyrolysis, are therefore sources of energy and consumers of energy; while the exothermic processes, such as maleic anhydride, phthalic anhydride, acrol and acrylic acid, ethylene oxide, formaldehyde, TD l / MDI, are exclusively sources of energy.
• Power source :
• the required electrical energy for the heat-consuming process can come from different sources at any time of the day, depending on the current supply of electricity. Three modes are possible: (i) exclusively from an external power source, in particular the public power grid, (ii) exclusively from at least one local power source or (iii) together from an external and at least one internal, local power source.
• all three modes (i), (ii) and (iii) can at least temporarily apply all of the energy required for the at least one heat-consuming process.
• 10 to 90% of the required energy preferably 25 to 75% of the required energy, particularly preferably 50% to 75% of the required energy, is taken from the external power source on an annual average.
• 10 to 90% of the required energy, 25 to 75%, particularly preferably 25% to 50% of the required energy is taken from the local power source on an annual average.
• At least 50% of the energy required for the heat-consuming process is advantageously provided by electrical energy, preferably at least 75%, more preferably at least 90%, in particular the energy required is provided exclusively electrically.
• the percentage range is advantageously 50 to 100, preferably 75 to 100, in particular 90 to 100.
• a continuous implementation advantageously takes longer than a day, preferably longer than a week, particularly preferably longer than a month, particularly preferably longer than two months, in particular longer than a six-month period, the process performance not more than 50% being preferred during this period not more than 30%, preferably not more than 20%, in particular not more than 10%, based on the maximum process performance.
• the percentage range is advantageously 50 to 0, preferably 30 to 0, more preferably 20 to 0, in particular 10 to 0.
• the process performance of the process according to the invention is advantageously based on the educt requirements of the downstream processes, i.e. the downstream implementation of the products from the heat-consuming process into further products.
• the local energy carrier networks advantageously have a total capacity greater than 5 GWh, preferably greater than 10 GWh, more preferably greater than 20 GWh, in particular greater than 50 GWh.
• the total capacity is advantageously in the range from 10 GWh to 1000 GWh, preferably from 20 GWh to 500 GWh, particularly preferably from 50 GWh to 200 GWh.
• the power grid is referred to as the external power source; this also includes a composite power plant; in particular a composite power plant with an approach time of more than 15 minutes.
• the term power grid refers to all or part of a network of transmission lines, substations and local distribution networks that transport and regulate electricity between the various physical nodes of the network as well as the various commercial, residential and large-scale consumers connected to the network are, enable.
• the difference between the external power source and the local, internal power source is that the electricity generated by the external power source is fed into a power grid from which many consumers can draw electricity.
• the local, internal power source is assigned to only a few chemical, heat-consuming processes, preferably 1 to 10 processes, more preferably 1 to 5 processes, in particular 1 to 3 processes.
• the electricity produced in the internal, local power source is transported through local power lines, which are operated independently of the general power grid in terms of frequency and voltage.
• the electricity produced in the internal, local power source is advantageously less than 20%, based on the total electrical energy produced in the internal power source, preferably less than 10% fed into the general power grid.
• the percentage range is advantageously 20 to 0, preferably 10 to 0. It is particularly preferred that the electricity produced in the internal, local electricity source is not fed into a general electricity network.
• the local power sources can deliver power to the external power grid.
• the local power sources can also be used as positive secondary control power or minute reserve power.
• the generation of electricity based on a gas turbine (GT) and / or a steam turbine (DT) and / or a fuel cell is advantageously considered as at least one local power source.
• Gas turbines are known to the person skilled in the art and are described, for example, in (C. Lechner, J. Seume (ed.): Stationäre Gasturbinen. Springer, Berlin 2003).
• Combustible raw materials and / or exhaust gas flows within the respective composite location and the respective process flows of the heat-consuming process, advantageously the starting materials and / or the products of the heat-consuming process, are advantageously considered as fuel for the gas turbine.
• a composite location of the chemical industry is a production facility with closed material and energy cycles in which production facilities, raw materials, chemical products, energy and waste flows, logistics and waste flows are networked with one another (www.basf.com/global/en/investors/calendar -and-publications / factbook / basf-group / verbund.html).
• a network location is characterized by a cascaded production chain. The variety of product substances increases along this cascade.
• a combined power plant typically has 3 stages: In the first stage the basic products are manufactured, in the second stage the intermediate products, in the third stage the specialty or end products. Each stage of this cascade can in turn consist of one or more stages.
• a Verbund site requires the import of a small number of raw materials, for example LPG, naphtha, light gasoline, residues from vacuum distillation, aromatics, sulfur, plus water and air and electrical energy in order to produce thousands of different chemical compounds and formulations from them.
• the numerical ratio of the products that are manufactured in a Verbund site and the raw materials used is greater than 10, preferably greater than 100, particularly preferably greater than 500.
• Hydrogen-rich waste gas flows are advantageous among combustible waste gas flows.
• Examples include exhaust gas streams from steam cracking, steam reforming, ammonia synthesis, methanol synthesis, formaldehyde synthesis, styrene production, coke production and steel production.
• These exhaust gas streams have different compositions and, depending on their origin, different designations, such as furnace gas, coke gas, dome gas, dehydrogenation gas, formalin gas, etc. (WO 2014/095661 A1).
• the common feature of these gases is their comparatively low calorific value compared to the calorific value of common fuels such as natural gas. Depending on the calorific value, gases are referred to as lean gases (calorific value up to approx.
• Fuel cells are described, for example, in (Hoogers, G. (Ed.). (2002). Fuel cell technology handbook. CRC press.), For example polymer electrolyte membrane fuel cell (PEMFC), phosphoric acid fuel cell (PAFC) , Alkaline fuel cells (AFC), molten carbonate fuel cells (MCFC) or solid electrolyte fuel cells (SOFC).
• PEMFC polymer electrolyte membrane fuel cell
• PAFC phosphoric acid fuel cell
• AFC Alkaline fuel cells
• MCFC molten carbonate fuel cells
• SOFC solid electrolyte fuel cells
• Oxy-fuel power plants that use oxygen-rich exhaust gas flows can also be considered as a local power source.
• electricity generation from steam turbines can be considered as a local electricity source.
• a hydrogen-powered gas turbine works advantageously with inlet temperatures of up to 1500 ° C and achieves an efficiency of up to 41%.
• a SOFC becomes beneficial operated at temperatures between 650 ° C and 1000 ° C and achieves an efficiency of up to 60%.
• An MCFC is advantageously operated at temperatures between 650 ° C and 1000 ° C and achieves an efficiency of up to 60%.
• a PEMFC works advantageously at temperatures between 50 ° C and 180 ° C and achieves an efficiency of up to 50%.
• An AFC works advantageously between 20 ° C and 80 ° C and achieves an efficiency of up to 70%.
• hydrocarbons are used as a source for local power generation, the following methods are particularly advantageous: gas turbine and / or SOFC and / or MCFC.
• a gas turbine operated with natural gas advantageously has an inlet temperature of up to 1230 ° C. and an efficiency of up to 39%.
• An SOFC is advantageously operated at temperatures between 650 ° C and 1000 ° C and achieves an efficiency of up to 60%.
• An SOFC is advantageously operated at temperatures between 550 ° C and 700 ° C and achieves an efficiency of up to 55%.
• the start-up time from standstill to full power is advantageously from 30 seconds to 30 minutes, preferably from 60 seconds to 20 minutes, particularly preferably from 90 seconds to 10 minutes (example: for the SIEMENS SGT-A65 a cold start time to full capacity ⁇ 7min specified).
• the output is advantageously from 40% to 120% of the nominal output, preferably from 50% to 110% of the nominal output, particularly preferably from 60% to 105% of the nominal output.
• the start-up time of a steam turbine from a standby state is advantageously 10 minutes to 60 minutes.
• the turbine is advantageously preheated to 300 ° C and rotated at a low speed (approx. 1 Hz) (Ref: Wikipedia “Steam turbine”).
• the output is advantageously from 10% to 120% of the nominal output, preferably from 20% to 110% of the nominal output, particularly preferably from 40% to 105% of the nominal output (Ref: Status report on flexibility requirements in the electricity sector, Chapter 4).
• the speed of a steam turbine can be regulated down to absolute idle, as long as the steam supply is ensured.
• the steam turbine is advantageously decoupled from the combustion, which supplies the energy for steam generation and steam overheating.
• the steam turbine can advantageously be fed from the existing steam network.
• various fuels can be used for steam generation.
• the steam can be stored in the voluminous steam network, e.g. 10 m3 to 100,000 m3, and thus buffer fluctuations in the availability of chemical energy.
• the steam turbine generator can advantageously be coupled directly or indirectly to generator types that generate hot exhaust gases, for example GT, SOFC or MCFC.
• Direct coupling means that the exhaust gas flow from the upstream generator is used to generate steam in the steam turbine, for example in a combined cycle power plant.
• Indirectly means that the exhaust gas flow from the upstream generator generates steam, which is fed into the steam network of the Verbund site.
• the steam turbine can be fed from this network.
• the start-up time of the PEMFC and the AFC is advantageously from 10 seconds to 15 minutes, preferably from 20 seconds to 10 minutes, particularly preferably from 30 seconds to 5 minutes.
• the PEMFC and the AFC have operating temperatures of around 80 ° C.
• the kinetics of the electrode reactions are already sufficient at room temperature to generate electrical power.
• waste heat can be used to advantage in order to keep the fuel cells at operating temperature without any problems.
• the C0 2 emissions caused by the operation of PEMFC and AFC are lower than 50 g C0 2 / kW e
• the PEMFC and AFC use hydrogen as a fuel before geous.
• the usable power range of the fuel cell generators is advantageously from 1% to 100% of the maximum output, preferably from 5% to 90% of the maximum output, particularly preferably from 10% to 70 % of the maximum output.
• the time to start or stop the local power source is advantageously shorter than the required response time of the minute reserve in electrical networks ( ⁇ 15 minutes), preferably shorter than the required response time of the secondary control ( ⁇ 5 minutes) and particularly preferably shorter than that Required response time of the primary control ( ⁇ 30 seconds).
• the following power sources reach full load from a standstill within 15 minutes: the gas turbine generator, the PEMFC generator and the AFC generator.
• the following power sources continue to reach full load within a start-up time of 5 minutes: PEMFC and AFC.
• a PEMFC generator or an AFC generator reach full load within 30 seconds, starting from 60% Fast, preferably 70% Fast, particularly preferably 80% Fast.
• an SOFC generator or an MCFC generator reach full load within 30 seconds, starting from 70% Fast, preferably 80% Fast, particularly preferably 90% Fast.
• Media that can be stored in a network location with sufficient capacity are advantageously used as energy carriers for operating the local power sources.
• these media are flammable liquid or gaseous raw materials, flammable gaseous or liquid basic products, for which a distribution network is available at the Verbund site, or non-reacting gaseous, liquid or solid energy carriers that can store mechanical energy, sensible heat or latent heat and can be distributed across the site.
• These media are preferably natural gas, liquefied gas or naphtha, hydrogen, ammonia, synthesis gas, compressed air, steam or regenerative solid storage.
• the media natural gas, hydrogen and water vapor are particularly preferred.
• Solid or liquid products are advantageously stored without pressure or with their own vapor pressure. This is due to the fact that liquids are quasi incompressible.
• Natural gas is advantageously transported in pipes under 50 bar.
• Hydrogen is advantageously stored in two pressure stages, at 40 bar and 325 bar, and distributed in the network.
• the high pressure is due to the fact that hydrogenations, as reactions that reduce the number of moles, are favored by high reaction pressures.
• Water vapor is advantageously stored at different pressure levels in order to use the pressure dependency of the boiling temperature / condensation temperature. Steam works as a heat transfer medium in the boiling point range. Due to the phase conversion, large amounts of heat can be absorbed (with evaporation) or given off (with condensation) with very good heat transfer without temperature change. For this reason, water vapor is stored at different pressure levels. An effective temperature range is assigned to each pressure level: 1.5 bar ⁇ 110 ° C
• the method according to the invention can be designed in different ways.
• This embodiment of the method according to the invention advantageously has one or two types of local current sources. If the method according to the invention has a type of local power source, this is advantageously a gas turbine generator, a Dampfturbi nengenerator, a PEMFC generator, an AFC generator, an SOFC generator or an MCFC generator.
• the one power source is preferably a steam turbine generator, a PEMFC generator or an AFC generator.
• the one power source is particularly preferably a steam turbine generator.
• the first power source is advantageously a gas turbine generator, a PEMFC generator, an AFC generator, an SOFC generator or an MCFC generator and the second power source is a steam turbine generator, the first being preferred Power source is a gas turbine generator, an SOFC generator or an MCFC generator and the second power source is a steam turbine generator, particularly preferably the first power source is a gas turbine generator and the second power source is a steam turbine generator. From each type of power source, one unit to ten units, preferably one unit to five units, particularly preferably one unit to two units, is assigned to a heat-consuming process.
• the steam turbine generator plays a special role.
• the steam turbine is advantageously supplied with steam from a locally arranged steam boiler, from the steam line of a locally arranged apparatus or from a steam network.
• the steam turbine preferably draws its steam from the steam network of the composite location.
• the drive steam for the steam turbine is permanently available and no longer limits the dynamics of the steam turbine generator such as the steam boiler or the steam line of the evaporative cooler.
• the steam network is advantageously fed from a central steam generator or from several steam generators that are distributed over the network location.
• the steam network is preferably fed from at least two steam generators. Particularly preferably, the steam network is fed via steam generators that are distributed in the composite location and that utilize local heat sources.
• Steam generators can be evaporative coolers of chemical reactors or steam boilers that use a fuel, a combustible exhaust gas flow or can also be electrically heated.
• the pressure in the steam network is advantageously from 4 bar to 200 bar, preferably from 6 bar to 150 bar, particularly preferably from 8 bar to 130 bar.
• the temperature in the network is advantageously from 150 ° C. to 700 ° C., preferably from 200 ° C. to 650 ° C., particularly preferably from 250 ° C. to 600 ° C.
• the volume of the steam network is advantageously from 1000 m3 to 10000000 m3, preferably from 5000 m3 to 5000000 m3, particularly preferably from 10,000 m3 to 2,000,000 m3.
• the internal energy of the steam stored in the steam network is advantageously from 1 MWh to 150,000 MWh, preferably from 10 MWh to 75,000 MWh, particularly preferably from 20 MWh to 50,000 MWh.
• This embodiment of the method according to the invention advantageously has one or two types of local current sources. If the method according to the invention has a type of local power source, this is advantageously a gas turbine generator, a Dampfturbi nengenerator, a PEMFC generator, an AFC generator, an SOFC generator or an MCFC generator.
• the one power source is preferably a PEMFC generator or an AFC generator.
• One power source is particularly preferably an AFC generator.
• the first power source is advantageously a gas turbine generator, a PEMFC generator, an AFC generator, an SOFC generator or an MCFC generator
• the second power source is a PEMFC generator or a AFC generator
• the first power source is a gas turbine generator, an SOFC generator or an MCFC generator
• the second power source is a PEMFC generator or an AFC generator
• the first power source is a gas turbine generator and the second power source AFC generator.
• one unit to ten units preferably one unit to five units, particularly preferably one unit to two units, is assigned to a heat-consuming process.
• the low-temperature fuel cells have a special function.
• the fuel cells are advantageously supplied from the hydrogen network of the Verbund site.
• Hydrogen is produced on an industrial scale through the gasification of coal, through the splitting of hydrocarbons, through partial oxidation, steam reforming or the autothermal reforming of natural gas, liquefied gas or naphtha, through the reforming of methanol, through the dehydrogenation of organic compounds, through water Electrolysis of water or produced by chlor-alkali electrolysis.
• the hydrogen is cleaned, compressed and introduced into the hydrogen network by pressure swing adsorption or by membrane processes.
• the BASF Verbund site in Fudwigshafen has a 40 bar and a 325 bar network for hydrogen.
• Fuel cells which are used as local power sources, can be operated in two modes: in normal mode as power generators or, in inverse mode, as hydrogen generators, where electrical current is used to split water into hydrogen and oxygen.
• the volume of the hydrogen network is advantageously from 100 m3 to 100,000 m3, preferably from 200 m3 to 50,000 m3, particularly preferably from 500 m3 to 20,000 m3.
• the heating energy stored in the hydrogen network is advantageously from 250 MWh to 250,000 MWh, preferably from 500 MWh to 120,000 MWh, particularly preferably from 1000 MWh to 50,000 MWh.
• This embodiment of the method according to the invention advantageously has one or two types of local current sources.
• a type of local power source this is advantageously a gas turbine generator, a steam turbine generator, an SOFC generator or an MCFC generator.
• the one power source is preferably a gas turbine generator or an SOFC generator.
• One power source is particularly preferably a gas turbine generator.
• the method according to the invention has two types of power source, the first power source is advantageously a gas turbine generator, an SOFC generator or an MCFC generator and the second power source is an SOFC generator or an MCFC generator, preferably the first power source is a gas turbine generator, and the second power source is a SOFC generator.
• one unit to ten units preferably one unit to five units, particularly preferably one unit to two units, is assigned to a heat-consuming process.
• the volume of the natural gas network is advantageously 1000 m3 to 1,000,000 m3, preferably from 2000 m3 to 500,000 m3, particularly preferably from 5000 m3 to 200,000 m3.
• the heating energy stored in the natural gas network is advantageously from 500 MWh to 500,000 MWh, preferably from 1000 MWh to 200,000 MWh, particularly preferably from 2000 MWh to 100,000 MWh.
• the method according to the invention controls the purchase of electrical energy advantageously with a load switch, which controls the switchover between the local and the external power source or an increase or throttle of one of the power sources.
• the proportion of the current sources can advantageously be set discretely and / or continuously. Diverter switches are known to those skilled in the art of electrical engineering.
• the switchover is advantageously carried out in discrete steps, in particular in the case of incapable local power sources. Alternatively, the switchover takes place continuously, especially in the case of local sources capable of partial loads.
• the electricity price is advantageously used as the control variable for the diverter switch.
• the required energy is taken from the external power source if the external power is cheaper than the locally produced power of the local power sources; For example, in times when so-called excess electricity and / or night-time electricity is available (night-time electricity is defined as electrical energy that is supplied at night - for example between 10 p.m. and 6 a.m. and has a low tariff).
• excess electricity is defined as the difference between the electrical power that could be produced at a given point in time with the available capacities and the electrical power that is consumed by the consumers.
• Surplus electricity is offered on the electricity market well below its production costs or at prices that are lower in terms of its energy content than for a fossil fuel with the same calorific value, or is offered for free (i.e. without consideration) or even at negative prices.
• At least 25%, particularly preferably at least 50%, of the electrical energy from the public power grid is provided by excess power and / or night power, preferably excess power.
• the required energy of the external power source is provided by excess power and / or night power.
• the entire energy of the external power source is provided by excess power and / or night power, preferably excess power.
• the power sources are advantageously changed while the heat-consuming process is being carried out.
• a change in the power sources is to be understood as connecting or disconnecting one or more local power sources or connecting or disconnecting the external power source, in particular the public power grid.
• a change in the current sources is to be understood as increasing or reducing the proportion of one of the current sources.
• the electrical energy supplied to the process advantageously decreases or fluctuates during the switchover by a maximum of 10% of the total power, preferably a maximum of 5% and in particular a maximum of 1%.
• the percentage range is advantageously 10 to 0, preferably 5 to 0, in particular 1 to 0.
• the small fluctuations can be achieved through the fast response times of the local power sources and the load switch. These response times are advantageously less than 30 minutes, preferably less than 15 minutes, particularly preferably less than 5 minutes.
• the heat-consuming process advantageously maintains its operating status during the switchover: the conversion of the heat-consuming process advantageously changes by a maximum of 2%, preferably a maximum of 1%, particularly preferably a maximum of 0.5%, in particular a maximum of 0 during the transition period , 2%.
• the change in energy sources advantageously changes the by-product selectivity of the high-temperature processes only slightly; the by-product selectivity preferably increases by a maximum of 1%, preferably by a maximum of 0.5%, in particular by a maximum of 0.2% (absolute).
• the endothermic process according to the invention is advantageously carried out in packed reactors, in tubular reactors or in arc reactors (see Henkel, KD (2000). Reactor types and their industrial applications. Ullmann's Encyclopedia of Industrial Chemistry).
• thermal energy for a heat-consuming process via electrical current examples include inductive or resistive processes, plasma processes, heating using electrically conductive heating elements / contact surfaces and / or microwaves.
• the direct electrical energy supply can take place inductively as well as resistively.
• the reactor walls or packings in the reactor space advantageously represent a corresponding resistance.
• the resistive variant is particularly preferred, since all electrical losses that arise from the end of the external power supply directly benefit the heating of the packs.
• the packs can be designed as a fluidized bed, moving bed or as a fixed bed.
• two or more electrodes are installed in the packs, between which the packs act as an electrical resistor and heat up when the current is passed through due to the electrical transmission losses.
• the flow of current can take place both transversely to the directions of flow of the packs and along them.
• electrical heating elements for example heating rods or heating cartridges, are arranged over the circumference of the reactor wall or embedded in the packs. These electrical heating elements heat up when current flows through them and give off this heat to the reactor wall or to the packing surrounding them.
• Heat transfer media such as flue gases, overheated vapors or melts.
• the sensible and / or latent heat contained in the heat carriers can be transferred to the packs or to the fluid process stream via built-in components such as heat transfer tubes or heat pipes.
• the reactor used for the process according to the invention advantageously contains a random packing of solid particles made of electrically conductive material.
• the packing can be structured homogeneously or vertically.
• a homogeneous packing can advantageously form a fixed bed, a moving bed or a fluidized bed.
• a pack structured in height forms It is advantageous to have a fixed bed in the lower section and a fluidized bed in the upper section.
• the structured packing advantageously forms a moving bed in the lower section and a fluidized bed in the upper section.
• the support materials of the reactor are advantageously temperature-resistant in the range from 500 to 2000 ° C., preferably from 1000 to 1800 ° C., more preferably from 1300 to 1800 ° C., particularly preferably from 1500 to 1800 ° C., in particular from 1600 to 1800 ° C.
• the carrier materials are advantageously electrically conductive in the range between 10 S / cm and 10 5 S / cm.
• the carrier materials advantageously have a volume-specific heat capacity of 300 to 5000 kJ / (m 3 K), preferably 500 to 3000 kJ / (m 3 K).
• carbonaceous materials e.g. Coke, silicon carbide and boron carbide can be considered.
• the supports are optionally coated with catalytic materials. These heat transfer materials can have a different expansion capacity compared to the carbon deposited on them.
• the carrier materials advantageously have a regular and / or an irregular geometric shape.
• Regularly shaped particles are advantageously spherical or cylindrical.
• the carrier materials advantageously have a grain size, i. an equivalent diameter, which can be determined by sieving with a certain mesh size, of 0.05 to 100 mm, preferably 0.1 to 50 mm, more preferably 0.2 to 10 mm, in particular 0.5 to 5 mm.
• the carrier materials are advantageously fed in countercurrent to the educt gases.
• the reaction space is expediently designed as a vertical shaft or shaft that widens from top to bottom, so that the movement of the moving bed occurs under the action of gravity.
• the carrier material can, however, also be passed through the reaction space as a fluidized bed. Both variants allow a continuous or quasi-continuous mode of operation.
• the heat transfer resistance during heat exchange between the gas and the solid packing in the heat transfer zones advantageously has a length of the transfer units or Fleight-of-Transfer Units (FITU) of 0.01 to 5 m, preferably 0.02 to 3 m, particularly preferably of 0.05 to 2 m, in particular from 0.1 to 1 m.
• FITU Fleight-of-Transfer Units
• the definition of FITU is taken from http: //elib.uni-stutt- gart.de/bitstream/11682/2350/l/docu_FU.pdf page 74.
• the heat capacity flow is the product of the mass flow and the specific heat capacity of a material flow.
• the ratio of the heat capacity flows is advantageously from 0.5 to 2, preferably from 0.75 to 1.5, particularly preferably from 0.85 to 1.2, in particular from 0.9 to 1.1.
• the ratio of the heat capacity flows is set via the feed flows and, if necessary, via the side feed or the side withdrawal of partial flows.
• the temperature of the support at the reactor inlet is advantageously between 0 and 300 ° C., preferably 10 and 150 ° C., in particular 50 to 100 ° C.
• the temperature of the educt gases at the reactor inlet is advantageously between 0 and 100 ° C, preferably 10 to 50 ° C.
• the method according to the invention is advantageously carried out with the aid of an electrically heated packaged pressure-bearing device, the device advantageously being divided into an upper, middle and lower device section.
• At least one vertically arranged pair of electrodes is advantageously installed in the middle section and all electrodes are advantageously arranged in an electrically conductive solid pack.
• the upper and lower device sections advantageously have a specific conductivity of 10 5 S / m to 10 8 S / m.
• the middle section of the device is advantageously electrically insulated from the solid pack.
• the upper and lower device sections are advantageously electrically insulated from the central device section.
• the upper electrode is advantageously connected via the upper device section and the lower electrode is advantageously connected via the lower device section or the electrodes are each connected via one or more connecting elements electrically contacted at these sections.
• the ratio of the cross-sectional area of the upper and lower electrode to the cross-sectional area of the respective electrically conductive connecting element or, without using a connecting element, the ratio of the cross-sectional area of the upper and lower electrode to the cross-sectional area of the respective electrically conductive device section is advantageously 0.1 to 10, preferably 0, 3 to 3, especially 0.5 to 2.
• the cross-sectional area of the electrode (e.g. the cross-sectional area of all electrode webs of a grid-shaped electrode) is advantageously in the range from 0.1 cm 2 to 10,000 cm 2 , preferably 1 cm 2 to 5000 cm 2 , in particular 10 cm 2 to 1000 cm 2 .
• the cross-sectional area of the current-conducting connection element or elements is advantageously in the range from 0.1 cm 2 to 10,000 cm 2 , preferably 1 cm 2 to 5000 cm 2 , in particular 10 cm 2 to 1000 cm 2 .
• the ratio of the cross-sectional area of the upper and / or lower electrode, preferably the upper and lower electrode, to the cross-sectional area of the respective electrically conductive device section is advantageously 0.1 to 10 , preferably 0.3 to 3, in particular 0.5 to 2.
• the cross-sectional area of the electrode is advantageously in the range from 0.1 cm 2 to 10,000 cm 2 , preferably 1 cm 2 to 5000 cm 2 , in particular 10 cm 2 to 1000 cm 2 .
• the cross-sectional area of the upper and / or lower device section is advantageously in the range from 0.1 cm 2 to 10,000 cm 2 , preferably 1 cm 2 to 5000 cm 2 , in particular 10 cm 2 to 1000 cm 2 .
• the reactor packing is advantageously designed as a moving bed. Accordingly, the reactor is advantageously divided into several zones. Advantageously, there are arranged from bottom to top: the outlet of the carrier, the gas inlet, the lower heat transfer zone, the lower electrode, the heated zone, the upper electrode with an optional side outlet, the upper heat transfer zone, the outlet of the gaseous product stream and the supply of the Carrier current.
• the lower heat transfer zone is the vertical distance between the upper edge of the gas inlet and the upper edge of the lower electrode.
• the upper heat transfer zone is the vertical distance between the lower end of the upper electrode and the upper end of the solid package.
• the heated zone at any point in the cross-section of the reactor is defined as the vertical distance between the lower end of the upper electrode and the upper end of the lower electrode.
• the lower side of the upper electrode and the upper side of the lower electrode are advantageously horizontal over the entire reactor cross-section. Consequently, the length of the heated zone, in particular the distance between the electrodes, is advantageously uniform over the entire reactor cross-section.
• the heated reactor cross section is advantageously from 0.005 m 2 to 200 m 2 , preferably from 0.05 m 2 to 100 m 2 , particularly preferably from 0.2 m 2 to 50 m 2 , in particular from 1 m 2 to 20 m 2 .
• the length of the heated zone is advantageously between 0.1 m and 100 m, preferably between 0.2 m and 50 m, particularly preferably between 0.5 m and 20 m, in particular between 1 m and 10 m.
• the ratio of the length to the equivalent diameter of the heated zone is advantageously from 0.01 to 100, preferably from 0.05 to 20, particularly preferably from 0.1 to 10, very particularly preferably from 0.2 to 5.
• the electrodes are advantageously positioned in the interior of the solid packing (see FIGS. 1 and 2).
• the vertical distance between the upper edge of the solid pack (the lowest point in the case of a slope) and the lower edge of the electrode plates or, without the use of electrode plates, the lower edge of the electrode webs on the upper electrode is advantageously from 10 mm to 5000 mm, preferably from 100 mm to 3000 mm, more preferably from 200 mm to 2000 mm.
• This section is advantageously from 1% to 50%, preferably from 2% to 20%, particularly preferably from 5% to 30% of the total height of the solid packing.
• the electrodes can take any shape known to those skilled in the art.
• the electrodes are designed as grids or rods.
• the electrodes preferably have a grid shape.
• Various design variants are conceivable for the grid shape, for example honeycomb grids are advantageously made of regular polygons, rectangular grids formed from parallel webs, spoke-shaped grids or grids made of concentric rings. Spoke-shaped grids with advantageously 2 to 30 webs arranged in a star shape and grids made of concentric rings are particularly preferred.
• the cross-sectional obstruction of the electrodes is advantageously between 1% and 50%, preferably between 1% and 40%, particularly preferably between 1% and 30%, in particular between 1% and 20%.
• an electrode in grid form which is attached to the inside of the upper or lower device section, e.g. a hood, or on a connecting element, e.g. an apron attached to the device section.
• a fixed bearing is understood to be the connection between a rigid body and its surroundings, with the aid of which a relative movement between the body and its surroundings is prevented in all directions.
• the electrode webs are advantageously connected at their outer end to the reactor hood or to the apron of the reactor hood.
• the contact area between the electrode and the reactor hood or skirt is advantageously between 0.1 cm 2 and 10,000 cm 2 , preferably between 1 cm 2 and 5000 cm 2 , in particular between 10 cm 2 and 1000 cm 2 .
• the ratio of the cross-sectional area of the skirt of the current-carrying reactor hood to the cross-section of the solid packing is advantageously 0.1% to 20%, preferably 0.2% to 10%, particularly preferably 0.5% to 5%.
• less than 5%, preferably less than 2%, preferably less than 1%, in particular 0.1% of the total electrical energy entered is dissipated in the hood-electrode unit.
• the range of the dissipated energy is preferably 0 to 5%, preferably 0 to 2%, in particular 0 to 1%.
• the material of the electrodes is advantageously iron, cast iron or a steel alloy, copper or a copper-based alloy, nickel or a nickel-based alloy, a refractory metal or an alloy based on refractory metals and / or an electrically conductive ceramic.
• the webs consist of a steel alloy, for example with the material number 1.0401, 1.4541, 1.4571, 1.4841, 1.4852, 1.4876 according to DIN EN10027-2 (issue date 2015-07), made of nickel-based alloys, for example with the material number 2.4816, 2.4642 Ti, in particular special alloys with the material numbers 3.7025, 3.7035, 3.7164, 3.7165, 3.7194, 3.7235.
• Zr, Hf, V, N b, Ta, Cr, Mo, W or alloys thereof are particularly advantageous; preferably Mo, W and / or N b or alloys thereof, in particular molybdenum and tungsten or alloys thereof.
• webs can contain ceramics such as silicon carbide and / or carbon, for example graphite, it being possible for the ceramics to be monolithic or fiber-reinforced composite materials (for example ceramic matrix compound, CMC, for example carbon fiber composite, CFC).
• the heat-consuming process is advantageously an endothermic high-temperature process, preferably a process whose energy consumption in the reaction zone is greater than 0.5 MW / m 3 , particularly preferably greater than 1 MW / m 3 , in particular greater than 2 MW / m 3 .
• the energy consumption can be between 0.5 and 10 MW / m 3 in the reaction zone.
• the heat-consuming processes are advantageous at an oxygen concentration of less than 5 vol .-%, in particular less than 2 vol. -%, in particular carried out without oxygen.
• the maximum temperature in the reaction zone is advantageously greater than 500 ° C., preferably greater than 800 ° C.
• the temperature in the reaction zone is in a range from 500 to 2500 ° C., preferably 700 to 1800 ° C .; for example at 500 to 800 ° C for dehydrogenation reactions, for example at 700 to 1000 ° C for reforming re actions, for example at 800 to 1100 ° C for steam cleavage reactions, for example at 800 to 1500 ° C for pyrolysis Reactions, for example at 800 to 1200 ° C in carbon gasification reactions.
• the following processes are advantageously considered as heat-consuming processes: the production of synthesis gas, of hydrogen, of styrene, of olefins, in particular ethylene, propylene and butene, of propene, of benzene, of acetylene, of, naphthalene, of carbon monoxide, of Hydrocyanic acid, nitrogen monoxide, hydrogen cyanide and / or pyrolysis carbon, as well as used in the calcination of aluminum hydroxide.
• Suitable carrier materials are, in particular, carbon-containing granules, silicon carbide-containing granules, nickel-containing metallic granules.
• Suitable carrier materials are, in particular, carbon-containing granulates. Production of olefins by splitting hydrocarbons in steam. Suitable carrier materials are, in particular, carbon-containing granules, silicon carbide-containing granules.
• Suitable support materials are, in particular, silicon carbide-containing granulates or iron-containing moldings coated with dehydrogenation catalysts.
• Suitable support materials are, in particular, silicon carbide-containing granulates or iron-containing moldings coated with dehydrogenation catalysts.
• Suitable support materials are, in particular, silicon carbide-containing granulates or iron-containing moldings coated with dehydrogenation catalysts.
• Aldehydes by catalytic dehydrogenation of alcohols, for example anhydrous formaldehyde from methanol.
• Suitable support materials are, in particular, silver-containing granules or silicon carbide-containing granules or iron-containing moldings coated with dehydrogenation catalysts.
• Suitable carrier materials are, in particular, carbon-containing granules.
• Suitable carrier materials are, in particular, silicon carbide-containing or iron-containing granules which are coated with a gap contact, for example a ferrite.
• Synthesis gas is advantageously used in downstream processes such as methanol synthesis, ammonia synthesis, oxo synthesis, Fischer-Tropsch synthesis (page “Synthesis gas”. In: Wikipedia, Die free Enzyklopadie. Status: March 10, 2020, 17:41 UTC. URF :
• the most important industrial olefins include ethylene, propylene and butenes.
• Ethylene is advantageously converted into secondary products such as polyethylene, ethylene dichloride, ethylene oxide, and ethylbenzene in downstream processes (page "Ethen”.
• butadiene is converted into secondary products such as synthetic rubber, acrylic-butadiene-styrene copolymers, adiponitrile (page “1,3-butadiene”.
• synthetic rubber acrylic-butadiene-styrene copolymers
• adiponitrile page “1,3-butadiene”.
• Hydrogen is advantageously used in downstream processes such as ⁇ (Häussinger, P., Lohmüller, R. and Watson, A. M. 2000. Hydrogen, 2. Production. Ullmann's Encyclopedia of Industrial Chemistry).
• Hydrocyanic acid is advantageously converted into secondary products such as adiponitrile, acetocyanhydrin, and cyanuric chloride in downstream processes (page “Hydrogen Cyanide”.
• adiponitrile acetocyanhydrin
• cyanuric chloride in downstream processes
• Carbon monoxide is advantageously converted into secondary products such as phosgene, formic acid, methyl formate, acetic acid and acetic anhydride in downstream processes.
• Formaldehyde is advantageously converted into secondary products such as 1,4-butanediol, methylenediphenyl isocyanate, polyoxymethylene, phenoplasts and aminoplasts in downstream processes (page "Formaldehyde”.
• Highly heat-consuming processes preferably high-temperature processes, in particular high-temperature processes in directly electrically heated packed reactors are particularly suitable for the use of electrical energy, since the conversion of electrical energy into heat is possible here with a high exergetic efficiency.
• Exergy is that Share of the internal energy of a system that can be converted into mechanical energy without increasing entropy. In general, when converting electrical energy into heat, a certain proportion of the exergy is destroyed. This proportion decreases with increasing temperature level of the heat sink, in the present case with increasing temperature of the strongly endothermic high temperature process.
• the products of the heat-consuming processes in particular hydrogen, synthesis gas and / or olefins, can advantageously be fed into a supply network of the composite site.
• the present invention also relates to a use of the method according to the invention as a load shedding capacity for the secondary control and / or as a minute reserve for the public power grid.
• the method according to the invention allows high-temperature methods to be used as load shedding capacity for the secondary control and / or as a minute reserve for frequency controls in electrical networks. With the method according to the invention, these high-temperature methods can be switched on quickly and can also draw high amounts of energy of 300 to 600 TWh. Operated continuously, these processes are permanently available for the feed-in of excess electricity, for example night electricity.
• the present invention enables a permanent decrease in excess electricity through continuously operated, electrically heated, heat-consuming processes.
• Large-scale chemical processes are thus available as load shedding capacity for secondary control and / or as a minute reserve. This can improve grid stability and significantly increase the utilization of regenerative energy sources.
• the profitability of the heat-consuming processes is improved by the fact that their load shedding capacity is remunerated for the network control.
• the present invention enables demand-controlled utilization of the heat-consuming processes, regardless of the availability of excess electricity in the general electricity network. This improves the ability to plan production in the downstream processes, and the storage requirement for high-quality, but also highly reactive and consequently dangerous intermediate products is minimized. In addition, the security of supply of the internal power sources is improved, as they are fed with energy sources from a network with high capacity and disruptions in individual processes are compensated for.
• the directly electrically heated moving bed reactors act as an ohmic load with a high heat capacity. This means that they can also be fed from sources that do not meet the specifications for feeding into the public grid.
• excess flow without intermediate storage ie almost loss-free, with an efficiency of advantageously greater than 90%, preferably greater than 95%, in particular greater than 98%, ie in a range of advantageously 95 to 100%, preferably 98 to 100%, for the heat-consuming process and thus to use its cost advantages without significant restrictions.
• the exergy loss when carrying out the method according to the invention is preferably less than 60%, preferably less than 50%, particularly preferably less than 40%, in particular less than 25% of the registered electrical energy.
• the underlying invention can thus serve as a technology platform for the transition to electrically driven chemical processes (energy transition). This provides the basis for the economically attractive use of excess electricity and provision of minute reserves. It is thus possible to reduce energy costs.
• a Verbund site has the infrastructure to store large quantities of energy sources such as natural gas, light petrol, hydrogen or water vapor and to use these without delay to drive suitable power sources.
• Hydrogen has the advantage that it can be used both as a basic product and as a universal storage medium for chemical energy. Hydrogen is suitable for driving both turbine generators and fuel cell generators. The generation of energy from hydrogen is free of C0 2 emissions.
• Pressurized hydrogen at 40 bar has a high energy density of around 57 kWh / m 3 compared to around 11 kWh / m 3 of steam at 500 ° C and 100 bar.
• Steam has the advantage that it can be used both as an energy store and as an operating medium for driving steam turbines.
• steam is used at various pressure levels to supply process engineering processes. At the BASF plant in Ludwigshafen, 2000 tons of steam are used per hour. This corresponds to an output of 1300 MW, which is approximately twice as high as the location's average electrical energy requirement. All fuels, combustible raw materials, combustible products, combustible exhaust gas streams, heat from solar collectors, and electrically generated heat can be used to generate steam.
• the pressure levels in the steam network the heat introduced can be converted into steam with high efficiency. In particular, when electricity is imported from the grid and the local power sources are switched off, the heat obtained from combustible exhaust gas flows can be stored in the steam network in the form of steam.
• FIG. 1 shows schematically a variant of the process according to the invention with a directly resistance-heated fluidized bed reactor, an inductively heated fixed bed reactor and an indirectly resistance-heated fixed bed reactor in a composite location.
• Each process is fed with electrical energy from both the general power grid and a local power source.
• FIG. 2 shows a diagram of the comparison process according to the prior art.
• the internal power source is a combined cycle power plant with steam export, which has the highest level of efficiency among conventional power plants.
• the steam turbine is connected directly to the waste heat boiler of the gas turbine generator.
• the response behavior of the steam turbine is determined by the inertia of the waste heat boiler of the gas turbine.
• FIG. 3 shows a diagram of the process according to the invention.
• the internal power source consists of a gas turbine generator and a steam turbine generator, identical to the combined cycle power plant.
• the steam turbine is not directly connected to the waste heat boiler of the gas turbine, but rather to the steam network of an integrated site. This means that the steam turbine can react to load changes with practically no delay.
• FIG. 4 shows a diagram of the process according to the invention.
• the heat-consuming process is fed from the general power grid and from local power sources.
• the local power sources are supplied with energy from the network.
• the network stores energy sources that are generated in the heat-consuming process and / or other processes within the network.
• the main products of the heat-consuming process are directed to a downstream process within the network.
• FIG. 5 shows a diagram of the process according to the invention.
• the heat-consuming process is fed from the general electricity grid and from a local power source.
• the local power source is supplied with water vapor from the network.
• Hydrogen which is a by-product of the heat-consuming process, is stored in the network.
• the local power source is driven by a steam turbine generator.
• the water vapor for this is drawn from the network.
• the main products of the heat-consuming process are directed to a downstream process within the network.
• Busbar for feeding electrical power from the internal power source
• Comparative process 2 Regenerative energy in electrolysis to hydrogen / reconversion in fuel cells to electrical energy
• electrical energy from the power grid can be used to generate hydrogen.
• the hydrogen can be fed into the pipeline network of the Verbund site.
• the hydrogen can be used as a material or, if necessary, converted back into electricity in a local fuel cell. Approx. 0.44 kJ of electrical energy can be recovered per kJ of electrical energy used in this process. This amount of electrical energy is free of C0 2 emissions.
• the amount of electrical energy that is produced using the method according to the invention is approximately 90% to 98% of the electrical energy that a process consisting of an electrolysis / fuel cell cycle and a combined cycle power plant (Eqs. 5, 12, 13).
• the main advantage of the invention is that imported electrical energy can be used to generate a multiple of electrical energy, free of CO 2 emissions, with the internal power sources.
• the amount of electrical energy used indicates the amount of energy related to 1 mol of methane that is imported into the network from the external power grid.
• the amount of electrical energy generated indicates the amount of energy related to 1 mole of methane that can be generated in the local power grid from the methane used and the previously used electrical energy or the products made from it.
• the amount of electrical energy that can be stored indicates the amount of energy related to 1 mole of methane that can be generated in the local power grid from products that have been produced in the network with the previously used electrical energy.
• AFC alkaline fuel cell
• NPP Thermal power plant powered by coal
• TKW thermal power plant
• VD Compressor
• Deionized water feed water for the waste heat boiler of the gas turbine

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• 2020
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